Transition metal complexes, ligands, catalysts for olefin polymerization, and process for production of olefin polymers

ABSTRACT

A transition metal complex represented by the formula (1): 
                         
wherein M is a Group 4 transition metal, A is a Group 16 element, B is a Group 14 element, n is an integer of 0 or 1, R 1 , R 2 , R 3  and R 4  may be the same or different and each independently denotes a substituent selected from the group consisting of the groups (I) and (II):
         group (I): hydrogen, alkyl and so on,   group (II): alkoxy, alkylthio and so on,
 
provided that at least one of R 1 , R 2 , R 3  and R 4  is a substituent selected from group (II);
 
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , X 1  and X 2  may be the same or different and are each hydrogen, halogen, alkyl or the like; and a catalyst for olefin polymerization comprising said complex, an organoaluminum compound and a boron compound are provided.

This application is a divisional of Ser. No. 10/503,252, filed Aug. 3,2004 now U.S. Pat. No. 7,141,690 which is a U.S. national stage ofInternational Application No. PCT/JP03/01215 filed Feb. 6, 2003.

TECHNICAL FIELD

The present invention relates to transition metal complexes, ligands,catalysts for olefin polymerization, and process for production ofolefin polymers.

BACKGROUND ART

Many production methods of olefin polymers by using metallocenecomplexes have already been reported. For example, JP-A 58-19309disclosed a method of producing olefin polymers using a metallocenecomplex and aluminoxane. However, such a method, in which olefinpolymerization is carried out catalytically by usingbis(cyclopentadienyl)zirconium dichloride and methylaluminoxane, had aproblem of the low molecular weight of the obtained olefin polymer. Toresolve the problem, JP-A 9-87313 disclosed polymerization usingdimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride. In such polymerization, the catalytic activity is high, butthere is still a need for further improvement in the molecular weightsof polymers to be obtained.

DISCLOSURE OF THE INVENTION

In consideration of the above-mentioned problems, the present inventionaims to provide transition metal complexes with excellent catalyticactivity and capable of providing polymers with high molecular weight,and a process of producing olefin polymers using them.

In order to accomplish the above-mentioned aims, the present inventorshad made investigations on transition metal complexes and catalysts forolefin polymerization, and finally found transition metal complexeshaving ligands comprising a cyclopentadiene ring having a heteroatom asa substituent and which ring is connected with a substituted benzenering via a covalent bond group, thereby the present invention wasaccomplished.

That is, the invention provides as follows:

1. a transition metal complex represented by the formula (1)

wherein M is a Group 4 transition metal;A is a Group 16 element;B is a Group 14 element;n is an integer of 0 or 1;R¹, R², R³ and R⁴ are the same or different and each independentlydenotes a substituent selected from the group consisting of thefollowing groups (I) and (II):

group (I) consisting of

hydrogen,

substituted or unsubstituted C₁₋₂₀ alkyl,

substituted or unsubstituted C₆₋₂₀ aryl,

substituted or unsubstituted C₇₋₂₀ aralkyl, and

silyl substituted with substituted or unsubstituted C₁₋₂₀ hydrocarbon,and

group (II) consisting of

substituted or unsubstituted C₁₋₂₀ alkoxyl,

substituted or unsubstituted C₆₋₂₀ aryloxy,

substituted or unsubstituted C₇₋₂₀ aralkyloxy,

silyloxy substituted with substituted or unsubstituted C₁₋₂₀hydrocarbon,

amino substituted with substituted or unsubstituted C₁₋₂₀ hydrocarbon,

phosphino substituted with substituted or unsubstituted C₁₋₂₀hydrocarbon, and

thio substituted with substituted or unsubstituted C₁₋₂₀ hydrocarbon,

provided that at least one of R¹, R², R³ and R⁴ is a

substituent group selected from the group (II);

R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are the same or different and eachindependently denotes hydrogen, halogen,

substituted or unsubstituted C₁₋₂₀ alkyl,

substituted or unsubstituted C₁₋₂₀ alkoxy,

substituted or unsubstituted C₆₋₂₀ aryl,

substituted or unsubstituted C₆₋₂₀ aryloxy,

substituted or unsubstituted C₇₋₂₀ aralkyl,

substituted or unsubstituted C₇₋₂₀ aralkyloxy,

silyl substituted with substituted or unsubstituted C₁₋₂₀ hydrocarbon,or

amino substituted with substituted or unsubstituted C₁₋₂₀ hydrocarbon;and

X¹ and X² are the same or different and each independently denoteshydrogen, halogen,

substituted or unsubstituted C₁₋₂₀ alkyl,

substituted or unsubstituted C₁₋₂₀ alkoxy,

substituted or unsubstituted C₆₋₂₀ aryl,

substituted or unsubstituted C₆₋₂₀ aryloxy,

substituted or unsubstituted C₇₋₂₀ aralkyl,

substituted or unsubstituted C₇₋₂₀ aralkyloxy, or

amino substituted with substituted or unsubstituted C₁₋₂₀ hydrocarbon;or

two adjacent substituents of R¹, R², R³ and R⁴, and two adjacentsubstituents of R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ may be each optionally bondedto form a ring;

2. a process of producing a transition metal complex represented by theformula (1) which comprises reacting substituted cyclopentadienerepresented by the formula (2):

wherein A, B, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are as definedabove, and R¹¹ is a substituted or unsubstituted hydrocarbon group or atrisubstituted silyl group, and the positions of the double bonds on thecyclopentadiene ring are optional or be a mixture of optional positions;with a base and then reacting with a transition metal compoundrepresented by the formula (3):

wherein M and n are as defined above;X¹, X², X³ and X⁴ are the same or different and each independentlydenotes hydrogen, halogen,substituted or unsubstituted C₁₋₂₀ alkyl,substituted or unsubstituted C₁₋₂₀ alkoxy,substituted or unsubstituted C₆₋₂₀ aryl,substituted or unsubstituted C₆₋₂₀ aryloxy,substituted or unsubstituted C₇₋₂₀ aralkyl,substituted or unsubstituted C₇₋₂₀ aralkyloxy, oramino substituted with substituted or unsubstituted C₁₋₂₀ hydrocarbon;3. substituted cyclopentadiene represented by the above-mentionedformula (2);4. a process of producing substituted cyclopentadiene represented by theabove-mentioned formula (2) which comprises reacting substitutedcyclopentadiene represented by the formula (5):

wherein R¹, R², R³ and R⁴ are as defined above, with a base and thenreacting with a compound represented by the formula (6):

wherein X⁵ is halogen and A, B, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are asdefined above;5. substituted cyclopentadiene represented by the above-mentionedformula (4):

wherein R¹² is hydrogen, substituted or unsubstituted C₁₋₂₀ alkyl orsubstituted or unsubstituted C₆₋₂₀ aryl;6. a catalyst for olefin polymerization comprising a transition metalcomplex represented by the above-mentioned formula (1) in combinationwith the following compound (A), wherein (A) is any one of or a mixtureof two or three of the following compounds (A1) to (A3):

(A1): an organoaluminum compound represented by the formula E1_(a)Al(Z)_((3-a)),

(A2): cyclic aluminoxane having the structure represented by the formula{—Al(E2)—O—}_(b),

(A3): linear aluminoxane having the structure represented by the formulaE3{—Al(E3)—O—}_(c)Al(E3)₂, wherein E1 to E3 are the same or differentand each independently denotes a C₁₋₈ hydrocarbon group, Z is the sameor different and each denotes hydrogen or halogen, a is an integer of 1,2 or 3, b is an integer of 2 or more, and c is an integer of 1 or more;

7. a catalyst of olefin polymerization comprising the transition metalcomplex represented by the above-mentioned formula (1) in combinationwith the following compounds (A) and (B), wherein (A) is any one of or amixture of two or three of the following compounds (A1) to (A3):

(A1): an organoaluminum compound represented by the formula E1_(a)Al(Z)_((3-a)),

(A2): cyclic aluminoxane having the structure represented by the formula{—Al(E2)—O—}_(b),

(A3): linear aluminoxane having the structure represented by the formulaE3{—Al(E3)—O—}_(c)Al(E3)₂, wherein E1 to E3 are the same or differentand each independently denotes a C₁₋₈ hydrocarbon group, Z is the sameor different and each denotes hydrogen or halogen, a is an integer of 1,2 or 3, b is an integer of 2 or more, and c is an integer of 1 or more,and (B) is any one of or a mixture of two or three of the followingcompounds (B1) to (B3):

(B1): a boron compound represented by the formula BQ1Q2Q3,

(B2): a boron compound represented by the formula Z⁺(BQ1Q2Q3Q4)⁻,

(B3): a boron compound represented by the formula (L-H)⁺(BQ1Q2Q3Q4)⁻,

wherein B is a boron atom in a trivalent valence state, Q1 to Q4 are thesame or different and each is a halogen atom, a C₁₋₂₀ hydrocarbon group,a C₁₋₂₀ halogenated hydrocarbon group, a substituted silyl group having1 to 20 carbon atoms, a C₁₋₂₀ alkoxy group or a disubstituted aminogroup having 2-20 carbon atoms, and L-H is a Bronsted acid; and8. a process of producing an olefin polymer which comprises polymerizingolefin in the presence of the catalyst for olefin polymerization asdescribed in the above 6 or 7.

MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in details.

With respect to transition metal complexes represented by the formula(1), the transition metal atom denoted by M is a Group 4 transitionmetal atom in the periodic table (IUPAC Inorganic Chemical Nomenclaturerevised in 1989) and it is, for example, a titanium atom, a zirconiumatom or a hafnium atom and preferably a titanium atom.

The element denoted by A is a Group 16 element in the periodic table andit is, for example, an oxygen atom, a sulfur atom or a selenium atom andpreferably an oxygen atom.

The element denoted by B is a Group 14 element in the periodic table andit is, for example, a carbon atom, a silicon atom or a germanium atomand preferably a silicon atom.

n denotes an integer of 0 or 1 and preferably 1.

The halogen atom denoted by R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, X¹and X² include a fluorine atom, a chlorine atom, a bromine atom and aniodine atom and a chlorine atom is preferably exemplified.

A substituent for the substituted C₁₋₂₀ alkyl denoted by R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, X¹ and X² includes halogen atoms. Specificexamples of the substituted or unsubstituted alkyl include, for example,methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl,n-pentyl, neopentyl, amyl, n-hexyl, heptyl, n-octyl, n-nonyl, n-decyl,n-dodecyl, n-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, n-eicosyl, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl,triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl,tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl,trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl,dibromoethyl, tribromoethyl, tetrabromoethyl, pentabromoethyl,perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl,perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl,perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl,perchlorooctyl, perchlorododecyl, perchloropentadecyl, perchloroeicosyl,perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl,perbromooctyl, perbromododecyl, perbromopentadecyl and perbromoeicosyland the preferable examples are methyl, ethyl, isopropyl, tert-butyl andamyl.

A substituent for the substituted C₇₋₂₀ aralkyl denoted by R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, X¹ and X² includes, for example, halogenatoms.

Specific examples of the substituted or unsubstituted C₇₋₂₀ aralkylinclude benzyl, (2-methylphenyl)methyl, (3-methylphenyl)methyl,(4-methylphenyl)methyl, (2,3-dimethylphenyl)methyl,(2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl,(2,6-dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl,(4,6-dimethylphenyl)methyl, (2,3,4-trimethylphenyl)methyl,(2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl,(3,4,5-trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl,(2,3,4,5-tetramethylphenyl)methyl, (2,3,4,6-tetramethylphenyl)methyl,(2,3,5,6-tetramethylphenyl)methyl, (pentamethylphenyl)methyl,(ethylphenyl)methyl, (n-propylphenyl)methyl, (isopropylphenyl)methyl,(n-butylphenyl)methyl, (sec-butylphenyl)methyl,(tert-butylphenyl)methyl, (n-pentylphenyl)methyl,(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl,(n-decylphenyl)methyl, (n-decylphenyl)methyl, naphthylmethyl andanthracenylmethyl. The preferable example is benzyl. All of thesearalkyl groups may be substituted with halogen such as fluorine,chlorine, bromine or iodine.

A substituent for the substituted C₆₋₂₀ aryl denoted by R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, X¹ and X² includes, for example, halogen atoms.

Specific examples of the substituted or unsubstituted C₆₋₂₀ aryl includephenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl,2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl,2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl,3,4,5-trimethylphenyl, 2,3,4,5-tetramethylphenyl,2,3,4,6-tetramethylphenyl, 2,3,5,6-tetramethylphenyl, pentamethylphenyl,ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl,sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl,n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl,n-tetradecylphenyl, naphthyl and anthracenyl and the preferable exampleis phenyl. All of these aryl groups may be substituted with halogen suchas fluorine, chlorine, bromine or iodine.

The substituted silyl denoted by R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ andR¹⁰ is a silyl group substituted with substituted or unsubstitutedhydrocarbon. Herein, the hydrocarbon includes C₁₋₁₀ alkyl such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl,isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl andn-decyl, and aryl such as phenyl. Specific examples of the substitutedsilyl having 1 to 20 carbon atoms include mono-substituted silyl having1 to 20 carbon atoms such as methylsilyl, ethylsilyl and phenylsilyl;di-substituted silyl substituted with C₁₋₂₀ hydrocarbon groups such asdimethylsilyl, diethylsilyl and diphenylsilyl; and tri-substituted silylsubstituted with C₁₋₂₀ hydrocarbon groups such as trimethylsilyl,triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl,tricyclohexylsilyl and triphenylsilyl, and the preferable examples aretrimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl. Thehydrocarbon groups constituting these substituted silyl groups may beunsubstituted groups as described above, or may be substituted withhalogen such as fluorine, chlorine, bromine or iodine.

A substituent for the substituted or unsubstituted C₁₋₂₀ alkoxy denotedby R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, X¹ and X² includes, forexample, halogen atoms. Specific examples of the substituted orunsubstituted C₁₋₂₀ alkoxy include methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy,neopentyloxy, n-hexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy,n-dodecyloxy, n-undecyloxy, n-dodecyloxy, tridecyloxy, tetradecyloxy,n-pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxyand n-eicosyloxy, and the preferable examples are methoxy, ethoxy andtert-butoxy. All of these alkoxy groups may be substituted with halogensuch as fluorine, chlorine, bromine or iodine.

A substituent for the substituted or unsubstituted C₇₋₂₀ aralkyloxydenoted by R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, X¹ and X² includes,for example, halogen atoms. Specific examples of the substituted orunsubstituted C₇₋₂₀ aralkyloxy include benzyloxy,(2-methylphenyl)methoxy, (3-methylphenyl)methoxy,(4-methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy,(2,4-dimethylphenyl)methoxy, (2,5-dimethylphenyl)methoxy,(2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy,(3,5-dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy,(2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy,(2,4,5-trimethylphenyl)methoxy, (2,4,6-trimethylphenyl)methoxy,(3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy,(2,3,4,6-tetramethylphenyl)methoxy, (2,3,5,6-tetramethylphenyl)methoxy,(pentamethylphenyl)methoxy, (ethylphenyl)methoxy,(n-propylphenyl)methoxy, (isopropylphenyl)methoxy,(n-butylphenyl)methoxy, (sec-butylphenyl)methoxy,(tert-butylphenyl)methoxy, (n-hexylphenyl)methoxy,(n-octylphenyl)methoxy, (n-decylphenyl)methoxy, naphthylmethoxy andanthracenylmethoxy, and the preferable example is benzyloxy. All ofthese aralkyloxy groups may be substituted with halogen such asfluorine, bromine, chlorine or iodine.

A substituent for the substituted C₆₋₂₀ aryloxy denoted by R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, X¹ and X² includes, for example, halogenatoms. Specific examples of the unsubstituted C₆₋₂₀ aryloxy includephenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy,2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy,2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy,2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy,2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy,2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy,2,3,5,6-tetramethylphenoxy, pentamethylphenoxy, ethylphenoxy,n-propylphenoxy, isoprylphenoxy, n-butylphenoxy, sec-butylphenoxy,tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy,n-tetradecylphenoxy, naphthoxy and anthracenoxy. Specific examples ofthe substituted C₆₋₂₀ aryloxy include, for example, the aboveunsubstituted C₆₋₂₀ aryloxy which is substituted with halogen such asfluorine, chlorine, bromine or iodine.

The amino substituted with C₁₋₂₀ hydrocarbon denoted by R¹, R², R³, R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, X¹ and X² is an amino substituted with twohydrocarbon groups. Herein, the hydrocarbon groups include, for example,C₁₋₂₀ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl and cyclohexyl, andaryl such as phenyl and these groups may be bonded with one another toform ring(s).

The amino substituted with C₁₋₂₀ hydrocarbon includes, for example,dimethylamino, diethylamino, di-n-propylamino, diisopropylamino,di-n-butylamino, di-sec-butylamino, di-tert-butylamino, diisobutylamino,tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino,di-n-decylamino, diphenylamino, bis(trimethylsilyl)amino,bis(tert-butyldimethylsilyl)amino, pyrrolyl, pyrrolidinyl, piperidinyl,carbozolyl, dihydroindolyl and dihydroisoindolyl, and the preferableexamples are dimethylamino, diethylamino, pyrrolydinyl and piperidinyl.

The silyloxy substituted with C₁₋₂₀ hydrocarbon denoted by R¹, R², R³and R⁴ is silyloxy substituted with three hydrocarbon groups. Herein,the hydrocarbon groups include, for example, as described above, C₁₋₂₀alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,tert-butyl, isobutyl, n-pentyl, n-hexyl and cyclohexyl, and aryl such asphenyl, and these groups may be bonded with one another to form ring(s).The substituted silyloxy having 1 to 20 carbon atoms includes, forexample, trimethylsilyloxy, triethylsilyloxy, tri-n-butylsilyloxy,triphenylsilyloxy, triisopropylsilyoxy, tert-butyldimethylsilyloxy,dimethylphenylsilyloxy and methyldiphenylsilyloxy and the preferableexamples are trimethylsilyloxy, triphenylsilyloxy andtriisopropylsilyloxy.

The phosphino substituted with C₁₋₂₀ hydrocarbon denoted by R¹, R², R³and R⁴ is phosphino substituted with two hydrocarbon groups. Herein, thehydrocarbon groups include C₁₋₂₀ alkyl such as methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl,cyclohexyl, heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl andn-eicosyl, and aryl such as phenyl, and these groups may be bonded withone another to form ring(s). Specific examples of the phosphinosubstituted with C₁₋₂₀ hydrocarbon include dimethylphosphino,diethylphosphino, di-n-propylphosphino, diisopropylphosphino,di-n-butylthio, di-sec-butylphosphino, di-tert-butylphosphino,di-isobutylphosphino, tert-butylisopropylphosphino, di-n-hexylphosphino,di-n-octylphosphino, di-n-decylphosphino, diphenylphosphino,bistrimethylsilylphosphino and bis-tert-butyldimethylsilylphosphino andthe preferably examples are dimethylphosphino, diethylphosphino anddiphenylphosphino.

Hydrocarbon groups for the thio substituted with C₁₋₂₀ hydrocarbondenoted by R¹, R², R³ and R⁴ include C₁₋₂₀ alkyl such as methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl,n-hexyl and cyclohexyl and aryl such as phenyl, and these groups may bebonded with one another to form ring(s) or thiophene. Specific examplesof such thio substituted with C₁₋₂₀ hydrocarbon include methylthio,ethylthio, n-propylthio, isopropylthio, n-butylthio, sec-butylthio,tert-butylthio, isobutylthio, n-hexylthio, n-octylthio, n-decylthio andphenylthio.

At least one of R¹, R², R³ and R⁴ is substituted or unsubstituted C₁₋₂₀alkoxy, substituted or unsubstituted C₆₋₂₀ aryloxy, substituted orunsubstituted C₇₋₂₀ aralkyloxy, silyloxy substituted with substituted orunsubstituted C₁₋₂₀ hydrocarbon, amino substituted with substituted orunsubstituted C₁₋₂₀ hydrocarbon, phosphino substituted with substitutedor unsubstituted C₁₋₂₀ hydrocarbon or thio substituted with substitutedor unsubstituted C₁₋₂₀ hydrocarbon.

Two adjacent substituents among R¹, R², R³ and R⁴, and two adjacentsubstituents among R⁶, R⁷, R⁸, R⁹ and R¹⁰ may be each optionally bondedto form ring(s).

As a ring formed by bond of two adjacent substituents of R¹, R², R³ andR⁴, for example, saturated or unsaturated hydrocarbon rings andheterocycles such as a furan ring, a thiophene ring and a pyrrole ringcan be exemplified.

An example of the transition metal complex represented by the formula(1) in which adjacent R³ and R⁴ are bonded to form a thiophene ring is,for example, a transition metal complex represented by the followingformula (7):

wherein M, A, B, R¹, R², R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, X¹, X² and n are asdefined for the formula (1), R¹³ and R¹⁴ are independently a substituentselected from the group (I) andthe bond moiety represented by

is a partial structure represented by the formula (7a):

wherein Y¹ and Y² are independently a carbon atom and Y³ is a sulfuratom, or by the formula (7b):

wherein Y¹ is a sulfur atom and Y² and Y³ are independently a carbonatom.

An example of the transition metal complex represented by the formula(1) in which adjacent R¹ and R² and adjacent R³ and R⁴ are each bondedto form a thiophene ring is a transition metal complex represented bythe following formula (8):

wherein M, A, B, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹³, X¹, X², Y¹, Y², Y³, R¹³,R¹⁴, the dotted line and n are as defined for the formulas (1) and (7),R¹⁵ and R¹⁶ are independently a substituent selected from the group (I)and the bond moiety represented by

is a partial structure represented by the formula (8a):

wherein Y⁴ and Y⁵ are independently a carbon atom and Y⁶ is a sulfuratom, or by the formula (8b):

wherein Y⁴ is a sulfur atom and Y⁵ and Y⁶ are independently a carbonatom.

As the ring formed by bond of two adjacent substituents among R⁶, R⁷,R⁸, R⁹ and R¹⁰, saturated or unsaturated hydrocarbon ring(s) which aresubstituted with substituted or unsubstituted C₁₋₂₀ hydrocarbon can beexemplified. Specific examples thereof include a cyclopropane ring, acyclobutane ring, a cyclopentane ring, a cyclohexane ring, acycloheptane ring, a cyclooctane ring, a benzene ring, a naphthalenering and an anthracene ring.

Specific examples of the transition metal complex represented by theformula (1) include, for example,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(2-[pyrrolidin-1-yl]-inden-1-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[piperidin-1-yl]-inden-1-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilyl(2-dimethylaminoinden-1-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(2-dimethylaminoinden-1-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(4,5-dimethyl-2-dimethylaminocyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(3,5-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[pyrrolidin-1-yl]-2-methylinden-1-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilyl(2-methoxyinden-1-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(2-methoxyinden-1-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(3-[dihydroisoindolin-2-yl]-inden-1-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(3-diphenylphosphinoinden-1-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(2,4,5-trimethyl-cyclopenta[2,3-b]thiophen-6-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, anddimethylsilyl(5-methyl-1-phenyl-cyclopenta[3,2-b]pyrrol-4-yl)(3,5-diamyl-2-phenoxy)titaniumdichloride; compounds obtained by replacing 2-phenoxy of the abovementioned compounds with 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxyor 3-tert-butyldimethylsilyl-2-phenoxy; compounds obtained by replacingdimethylsilyl of the above mentioned compounds with diethylsilyl,diphenylsilyl or dimethoxysilyl; compounds obtained by replacingtitanium of the above mentioned compounds with zirconium or hafnium;compounds obtained replacing chloride of the above mentioned compoundswith bromide, iodide, dimethylamide, diethylamide, methoxide,n-butoxide, isopropoxide, methyl or benzyl; and transition metalcomplexes represented by the formula (1) in which B is a Group 14element in the periodic table other than silicon.

Such a transition metal complex (1) may be produced by, for example,reacting the substituted cyclopenadiene represented by the formula (2)with a base and then with a transition metal compound represented by theformula (3).

Of the substituted or unsubstituted hydrocarbon group denoted by R¹¹ theunsubstituted hydrocarbon group includes C₁₋₁₀ alkyl such as methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl;C₂₋₁₀ alkenyl such as vinyl, allyl, propenyl, 2-methyl-2-propenyl,homoallyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl and decenyl;and C₇₋₁₂ aralkyl such as benzyl, (4-methylphenyl)methyl and(2,4,6-trimethylphenyl)methyl. The substituted hydrocarbon groupincludes alkoxyalkyl such as methoxymethyl or methoxyethoxymethyl andfurther, halogen-substituted hydrocarbon groups, which hydrocarbongroups are the above mentioned unsubstituted hydrocarbon groups, whoseexample is 2-chloro-2-propenyl.

The tri-substituted silyl group includes trimethylsilyl, triethylsilyl,tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl,tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl,tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl,tricyclohexylsilyl and triphenylsilyl. Among such substituents denotedby R¹¹, alkenyl, particularly allyl is preferred in terms of high yieldin production of the transition metal complex represented by the formula(1)

The hydrogen, halogen, substituted or unsubstituted C₁₋₂₀ alkyl,substituted or unsubstituted C₇₋₂₀ aralkyl, substituted or unsubstitutedC₆₋₂₀ aryl, silyl substituted with substituted or unsubstituted C₁₋₂₀hydrocarbon, substituted or unsubstituted C₁₋₂₀ alkoxy, substituted orunsubstituted C₁₋₂₀ aralkyloxy, substituted or unsubstituted C₁₋₂₀aryloxy and di-substituted amino having 2 to 20 carbon atoms denoted byX³ or X⁴ include those exemplified as X¹ and X² in the transition metalcomplex represented by the formula (1).

The base that may be used for production of the compound represented bythe formula (1) includes organic alkali metal compounds, for example,organolithium compounds such as methyl lithium, ethyl lithium, n-butyllithium, sec-butyl lithium, tert-butyl lithium, lithiumtrimethylsilylacetylide, lithium acetylide, trimethylsilylmethyllithium, vinyl lithium, phenyl lithium and allyl lithium. The usedamount of the base is generally in a range of 0.5 to 5 moles per 1 moleof the compound (2).

Further, the base may be used in combination with an amine compound.Such an amine compound includes primary amine compounds such asmethylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,tert-butylamine, n-octylamine, n-decylamine, aniline andethylenediamine, secondary amine compounds such as dimethylamine,diethylamine, di-n-propylamine, di-n-butylamine, di-tert-butylamine,di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane anddiphenylamine, and tertiary amine compounds such as trimethylamine,triethylamine, tri-n-propylamine, tri-n-butylamine,diisopropylethylamine, tri-n-octylamine, tri-n-decylamine,triphenylamine, N,N-dimethylaniline,N,N,N′,N′-tetramethylethylenediamine, N-methylpyrrolidine and4-dimethylaminopyridine. The used amount of such an amine compound isgenerally in a range of 10 moles or less, preferably 0.5 to 10 moles,more preferably 1 to 3 moles per 1 mole of the base.

The reaction is generally carried out in an inert solvent. Such asolvent includes aprotic solvents, for example, aromatic hydrocarbonsolvents such as benzene or toluene, aliphatic hydrocarbon solvents suchas hexane or heptane, ether solvents such as diethyl ether,tetrahydrofuran or 1,4-dioxane, amide solvents such ashexamethylphosphoric amide or dimethylformamide, polar solvents such asacetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutylketone and cyclohexanone, and halogenated solvents such asdichloromethane, dichloroethane, chlorobenzene or dichlorobenzene. Thesesolvents may be used alone or as a mixture of two or more of them andthe used amount is generally in range of 1 to 200 parts by weight,preferably 3 to 50 parts by weight per 1 part by weight of substitutedcyclopentadiene represented by the formula (2).

This reaction may be generally carried out by adding substitutedcyclopentadiene represented by the formula (2) and the base to thesolvent and then adding the transition metal compound represented by theformula (3). A solid that may be precipitated after adding substitutedcyclopentadiene represented by the formula (2) and the base to thesolvent may be removed from the reaction system and then added to thesame solvent as described above and then the transition metal compoundrepresented by the formula (3) may be added thereto. Alternatively,substituted cyclopentadiene represented by the formula (2), the base andthe transition metal compound represented by the formula (3) may beadded simultaneously. The reaction temperature is generally −100° C. orhigher to the boiling point of the solvent or lower, preferably in arange of −80 to 100° C. It is preferable that the reaction system isshielded from light in terms of the yield of the transition metalcomplex represented by the formula (1).

From the reaction mixture thus obtained, the aimed transition metalcomplex represented by the formula (1) can be obtained by a conventionalmethod, for example, by filtrating off a produced precipitate,concentrating the filtrate to produce a transition metal complexrepresented by the formula (1), and then separating it by filtration.

The substituted cyclopentadiene represented by the formula (2) isproduced, for example, by reacting substituted cyclopentadienerepresented by the formula (5):

wherein R¹, R², R³ and R⁴ are as defined above, with a base and thenreacting with a compound represented by the formula (6):

wherein X⁵ is halogen, and A, B, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are asdefined above.

This step is generally carried out by adding the compound (5) and a baseto a solvent and then adding the compound (6) thereto. The reactiontemperature is generally in a range from −100° C. to the boiling pointof a solvent. In the case that an organic alkali metal compound is usedas the base, it is preferably in a range of −80 to 40° C.

Such a base is not particularly limited and includes organic alkalimetal compounds, for example, organolithium compounds such as methyllithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyllithium, lithium trimethylsilylacetylide, lithium acetylide,trimethylsilylmethyl lithium, vinyl lithium, phenyl lithium and allyllithium, and inorganic bases such as sodium hydride, potassium hydride,sodium methoxide and potassium butoxide. The used amount of the base isgenerally in a range of 0.5 to 5 moles per 1 mole of the compound (2).

The reaction mixture containing the compound (2) thus obtained may beused as it is in a solution form in the next step or after adding wateror an aqueous acidic solution to the mixture, separating the organiclayer, drying it and then removing the solvent by distillation.Preferably, after the reaction mixture thus obtained is distilled underreduced pressure to remove the solvent, a hydrocarbon solvent is addedto the residue, insoluble substances are filtered off and the resultingfiltrate is concentrated under reduced pressure to obtain a residue,which is used in the next step. The compound (2) thus obtained may befurther purified by recrystallization, distillation, columnchromatography, or the like.

Specific examples of the substituted cyclopentadiene represented by theformula (2) include, for example,(2-allyloxyphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxyphenyl)(2-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(2-[pyrrolidin-1-yl]]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(2-[pyrrolidin-1-yl]]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(2-[pyrrolidin-1-yl]]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(2-[pyrrolidin-1-yl]]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(2-[pyrrolidin-1-yl]]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(2-[pyrrolidin-1-yl]]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(2-[pyrrolidin-1-yl]]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(2-[pyrrolidin-1-yl]]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(2-[pyrrolidin-1-yl]]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(2-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(2-[pyrrolidin-1-yl]]-1H-inden-1-yl)dimethylsilane,(2-allyloxyphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(3-[piperidin-1-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxyphenyl)(2-dimethyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(2-dimethylamino-1H-inden-1-yl)dimethylsilane,(2-allyloxyphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxy-3-methylphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(4,5-dimethyl-2-dimethylaminocyclopentadienyl)dimethylsilane,(2-allyloxyphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(3-[pyrrolidin-1-yl]-2-methyl-1H-inden-1-yl)dimethylsilane,(2-allyloxyphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(2-methoxyl-1H-inden-1-yl)dimethylsilane,(2-allyloxyphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(1-allyloxynaphthalen-2-yl)(3-[dihydroisoindolin-2-yl]-1H-inden-1-yl)dimethylsilane,(2-allyloxyphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(1-allyloxynaphthalen-2-yl)(3-diphenylphosphino-1H-inden-1-yl)dimethylsilane,(2-allyloxyphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(1-allyloxynaphthalen-2-yl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxyphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(1-allyloxynaphthalen-2-yl)(2,5-dimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane,(2-allyloxyphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(1-allyloxynaphthalen-2-yl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane,(2-allyloxyphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(2-allyloxy-3-methylphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(2-allyloxy-3,5-dimethylphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(2-allyloxy-3-tert-butylphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methylphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(2-allyloxy-3,5-di-tert-butylphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(2-allyloxy-5-methyl-3-phenylphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(2-allyloxy-5-methyl-3-trimethylsilylphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(2-allyloxy-3-tert-butyldimethylsilyl-5-methylphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(2-allyloxy-3,5-diamylphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(2-allyloxy-3-tert-butyl-5-methoxyphenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,(6-allyloxy-5-tert-butyl-3-chlorophenyl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane,and(1-allyloxynaphthalen-2-yl)(5-methyl-1-phenyl-4-hydrocyclopenta[3,2-b]pyrrol-4-yl)dimethylsilane;compounds obtained by replacing allyloxy of the above mentionedcompounds with methoxy, benzyloxy, ethoxy, trimethylsilyloxy,tert-butyldimethylsilyloxy or methoxymethoxy; compounds obtained byreplacing dimethysilane of the above mentioned compounds withdiethylsilane, diphenylsilane or dimethoxysilane; compounds obtained byreplacing 2-allyloxyphenyl of the above mentioned compounds with3-phenyl-2-allyloxyphenyl, 3-trimethylsilyl-2-allyloxyphenyl or3-tert-butyldimethylsilyl-2-allyloxyphenyl; and cyclopentadienylcompounds represented by the formula (2) in which B is a Group 14element in the periodic table other than silicon.

The transition metal compound represented by the formula (3) includes,for example, titanium halides such as titanium tetrachloride, titaniumtrichloride, titanium tetrabromide, or titanium tetraiodide,amidotitnaium such as tetrakis(dimethylamino)titanium,dichlorobis(dimethylamino)titanium, trichloro(dimethylamino)titanium ortetrakis(diethylamino)titanium, and alkoxytitanium such astetraisopropoxytitanium, tetra-n-butoxytitanium,dichlorodiisopropoxytitnaium and trichloroisopropoxytitanium andcompuonds obtained by replacing titanium of the above mentionedcompounds with zirconium or hafnium, and the preferable example istitanium tetrachloride. The used amount of the transition metal compoundrepresented by the formula (3) is generally in a range of 0.5 to 3moles, preferably 0.7 to 1.5 moles per 1 mole of substitutedcyclopentadiene represented by the formula (2).

The substituted cyclopentadiene represented by the formula (4) may beproduced, for example, by reacting2,5-dimethyl-5,6-dihydrocyclopenta[1,2-b]thiophen-4-one with an alkylmetal or an aryl metal compound to obtain alcohol and then dehydratingsaid alcohol. According to a procedure similar to a well-known synthesismethod of pyrrole analogous compounds (J. Am. Chem. Soc., 2001, vol.123, p. 4763), 2,5-dimethyl-5,6-dihydrocyclopenta[1,2-b]thiophen-4-onecan be produced from 5-methyl-2-thiophenecarboxamide.

For the substituted cyclopentadiene represented by the formula (5), forexample, WO 01/47939 discloses a synthesis method of cyclopentadienecompounds substituted with sulfur and WO 01/53360 and WO 00/66596disclose synthesis methods of cyclopentadiene compounds substituted withnitrogen. Further, WO 01/53361 discloses cyclopentadiene compoundssubstituted with silicon.

For use in polymerization reaction, the transition metal complexrepresented by the formula (1) thus produced and the compound (A) orsaid transition metal complex, the compound (A) and the compound (B) maybe added in optional order to a reaction system. Alternatively, saidtransition metal complex and the compound (A) or said transition metalcomplex, the compound (A) and the compound (B) may be contactedpreviously and the resulting reaction mixture may be used inpolymerization reaction.

[Compound (A)]

As the compound (A) that may be employed in the present invention, forexample, a well-known organoaluminum compound can be used. As thecompound (A), a well-known organoaluminum compound is preferably usedand more preferred example is any one of or a mixture of two or three ofthe following compounds (A1) to (A3).

(A1): an organoaluminum compound represented by the formula E1_(a)Al(Z)_((3-a));

(A2): cyclic aluminoxane having the structure represented by the formula{—Al(E2)—O—}_(b);

(A3): linear aluminoxane having the structure represented by the formulaE3{—Al(E3)—O—}_(c)Al(E3)₂; wherein E1 to E3 are the same or differentand each independently denotes C₁₋₈ hydrocarbon, Z is the same ordifferent and denotes hydrogen or halogen, a denotes 1, 2, or 3, bdenotes an integer of 2 or more, and c denotes an integer of 1 or more.

Specific examples of the organoaluminum compound (A1) represented by theformula E1aAl(Z)_((3-a)) include, for example, trialkylaluminum such astrimethylaluminum, triethylaluminum, tripropylaluminum,triisobutylaluminum or trihexylaluminum; dialkylaluminum chloride suchas dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminumchloride, diisobutylaluminum chloride or dihexylaluminum chloride;alkylaluminum dichloride such as methylaluminum dichloride,ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminumdichloride or hexylaluminum dichloride; dialkylaluminum hydride such asdimethylaluminum hydride, diethylaluminum hydride, dipropylaluminumhydride, diisobutylaluminum hydride or dihexylaluminum hydride. Thepreferable example is trialkylaluminum and the more preferable examplesare triethylaluminum and triisobutylaluminum.

In the cyclic aluminoxane (A2) represented by the formula{—Al(E2)—O—}_(b) and the linear aluminoxane (A3) represented by theformula E3{—Al(E3)—O—}_(c)Al(E3)₂, specific examples of E2 and E3 arealkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, n-pentyl and neopentyl, b denotes an integer of 2 or more andc denotes an integer of 1 or more. Preferably, E2 and E3 are methyl orisobutyl, b is an integer of 2 to 40 and c is an integer of 1 to 40.

The above-mentioned aluminoxane is produced by a variety of methods.Such methods are not particularly limited and the aluminoxane may beproduced in a similar manner to a known method in the art. For example,the aluminoxane is produced by dissolving trialkylaluminum (e.g.trimethylaluminum) in a suitable organic solvent (e.g. benzene, analiphatic hydrocarbon, and the like) and then contacting said solutionwith water. In addition, a production process thereof by bringingtrialkylaluminum (e.g. trimethylaluminum) into contact with a metal saltcontaining crystal water (e.g. copper sulfate hydrate) is alsoexemplified.

[Compound (B)]

As the compound (B) that may be employed in the present invention, anyone of or a mixture of two or three of (B1) the boron compoundrepresented by the formula BQ1Q2Q3, (B2) the boron compound representedby the formula Z⁺(BQ1Q2Q3Q4)⁻ or (B3) the boron compound represented bythe formula (L-H)⁺(BQ1Q2Q3Q4)⁻ can be exemplified.

In (B1) the boron compound represented by the formula BQ1Q2Q3, B isboron in trivalent valence state and Q1 to Q3 independently denote ahalogen atom, a C₁₋₂₀ hydrocarbon group, a halogenated C₁₋₂₀ hydrocarbongroup, a substituted silyl group having 1 to 20 carbon atoms, a C₁₋₂₀alkoxy group or a di-substituted amino group having 2 to 20 carbonatoms, which may be the same or different from one another. Preferableexamples of Q1 to Q3 are a halogen atom, a C₁₋₂₀ hydrocarbon group and ahalogenated C₁₋₂₀ hydrocarbon group.

Specific examples of (B1) include tris(pentafluorophenyl)borane,tris(2,3,5,6-tetrafluorophenyl)borane,tris(2,3,4,5-tetrafluorophenyl)borane,tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane andphenylbis(pentafluorophenyl)borane, and the preferable example istris(pentafluorophenyl)borane.

In (B2) the boron compound represented by the formula Z⁺(BQ1Q2Q3Q4)⁻, Z⁺denotes an inorganic or organic cation, B is boron in trivalent valencestate, and Q1 to Q4 are the same as those denoted by Q1 to Q3 in theabove-mentioned (B1).

In specific examples of the compound represented by the formulaZ⁺(BQ1Q2Q3Q4)⁻, the inorganic cation Z⁺ includes a ferrocenium cation,an alkyl-substituted ferrocenium cation and a silver cation; the organiccation Z⁺ includes a triphenylmethyl cation; and (BQ1Q2Q3Q4)⁻ includestetrakis(pentafluorophenyl)borate,tetrakis(2,3,5,6-tetrafluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,tetrakis(2,2,4-trifluorophenyl)borate,phenylbis(pentafluorophenyl)borate andtetrakis(3,5-bistrifluoromethylphenyl)borate.

Specific combinations of them include ferroceniumtetrakis(pentafluorophenyl)borate, 1,1′-dimethylferroceniumtetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis(pentafluorophenyl)borate and triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate, and the preferred exampleis triphenylmethyl tetrakis(pentafluorophenyl)borate.

In (B3) the boron compound represented by the formula(L-H)⁺(BQ1Q2Q3Q4)⁻, L is a neutral Lewis base, (L-H)⁺ is a Bronstedacid, B is boron in trivalent valence state and Q1 to Q4 are the same asthose denoted by Q1 to Q3 in the above-mentioned formula (B1).

In specific examples of the compound represented by the formula(L-H)⁺(BQ1Q2Q3Q4)⁻, a Bronsted acid denoted by (L-H)⁺ includestrialkyl-substituted ammonium, N,N-dialkylanilinium, dialkylammonium andtriarylphosphonium and examples of (BQ1Q2Q3Q4)⁻ are as defined above.

Specific combinations of them include triethylammoniumtetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bistrifluoromethylphenyl)borate, diisopropylammoniumtetrakis(pentafluorophenyl)borate, dicyclohexylammoniumtetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate and tri(dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate and the preferred examples aretri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate andN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate.

With respect to the amount of each catalytic component that may be used,it is desirable to use each catalytic component so that the molar ratioof the compound (A)/the transition metal complex (1) is in a range of0.1 to 10,000, preferably 5 to 2,000 and the molar ratio of the compound(B)/the transition metal complex (1) is in a range of 0.01 to 100,preferably 0.5 to 10.

With respect to the concentration of each catalytic component in thecase of using it in a solution form, it is desirable that the transitionmetal complex represented by the formula (1) is used in a range of0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L; the compounds (A) isused in a range of 0.01 to 500 mmol/L, preferably 0.1 to 100 mmol/L onthe basis of Al atom; and the compounds (B) is used in a range of 0.0001to 5 mmol/L, preferably 0.001 to 1 mmol/L.

Monomers employed for polymerization in the present invention may beolefin or diolefin having 2 to 20 carbon atoms and two or more kinds ofmonomers may be used simultaneously. The following are examples of suchmonomers, but the present invention is not limited to these exemplifiedcompounds. Specific examples of such olefin include, for example,ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1,nonene-1, decene-1,5-methyl-2-pentene-1, vinylcyclohexene, 2-norbornene,cyclohexene and dicyclopentadiene. Diolefin compounds may be conjugateddiene or non-conjugated diene of hydrocarbon compounds and specificexamples thereof include the non-conjugated diene compounds such as1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene,1,8-nonadiene, 1,9-decadiene, 4-methyl-1,4-hexadiene,5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene,5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene,5-methyl-2-norbornene, norbornadiene, 5-methylene-2-norbornene,1,5-cyclooctadiene or 5,8-endomethylenehexahydronaphthalene, and theconjugated diene compounds such as 1,3-butadiene, isoprene,1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene or 1,3-cyclohexadiene.Specific examples of monomers constituting a copolymer include ethyleneand propylene; ethylene and butene-1; ethylene and hexene-1; propyleneand butene-1; and combinations of the above mentioned combinations and5-ethylidien-2-norbornene, but the present invention is not limited tothe above-mentioned compounds.

In the present invention, aromatic vinyl compounds may be also used as amonomer. Specific examples of the aromatic vinyl compounds includestyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene,o-chlorostyrene, p-chlorostyrene, α-methylstyrene and divinylbenzene.

A method for polymerization is not specifically limited, and forexample, may be solvent polymerization or slurry polymerization, inwhich aliphatic hydrocarbon such as butane, pentane, hexane, heptane oroctane, aromatic hydrocarbon such as benzene or toluene, or halogenatedhydrocarbon such as methylene dichloride is used as a solvent, or gasphase polymerization in a gaseous monomer, which may be eithersuccessive polymerization or batch polymerization.

The polymerization temperature is generally in a range of −50° C. to250° C. and in order to produce polymers with high molecular weights, itis particularly preferable in a range of −20° C. to 100° C. Thepolymerization pressure is preferably from the normal pressure (e.g.about 0.1 MPa) to 10 MPa (100 kg/cm² G). From an industrial viewpoint,high temperature and high pressure polymerization at 100° C. or higherand 10 MPa or higher is sometimes preferable, and such high temperatureand high pressure polymerization may be applicable to the presentinvention. In general, the polymerization time is appropriatelydetermined depending on the types of the aimed polymers and reactionapparatus and it may be generally in a range of 1 minute to 20 hours. Inthe present invention, a chain transfer agent such as hydrogen may beadded to control the molecular weight of a copolymer.

EXAMPLES

The following Examples will illustrate the present invention in details,but they are not intended to limit the present invention.

The following abbreviations are used in Tables 1 to 6.

TIBA: triisobutylaluminum

MMAO: Modified methyl aluminoxane (methylaluminoxane modified byaddition of triisobutylaluminum)

AB: dimethylanilinium tetrakis(pentafluorophenyl)borate

CB: triphenylmethyl tetrakis(pentafluorophenyl)borate

PE: polyethylene

Tm: the melting point of a polymer

Mw: the molecular weight of a polymer

Mw/Mn: the molecular weight distribution of a polymer

SCB: the number of methyl branches per 1,000 carbon atoms of a polymer

Example 1 Synthesis of(2-allyloxy-3-tert-butyl-5-methylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane

A solution of(2-allyloxy-3-tert-butyl-5-methylphenyl)chlorodimethylsilane (0.82 g,2.49 mmol) in toluene (4.1 mL) was added dropwise to a solution of3-(3-[pyrrolidin-1-yl]-1H-inden-1-yl)lithium (0.50 g, 2.62 mmol)tetrahydrofuran (5.6 mL) at 0° C. The resulting reaction mixture waswarmed to room temperature and stirred for 18 hours. After the solventwas distilled off under reduced pressure, hexane (20.0 mL) was added andthe mixture was filtered to remove insoluble substances. The filtratewas distilled under reduced pressure to quantitatively obtain(2-allyloxy-3-tert-butyl-5-methylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane.

¹H-NMR (deuterated benzene, δ(ppm)): 0.15-0.20(6H), 1.41(9H),1.46-1.50(4H), 2.10(3H), 3.09-3.14(4H), 3.93(1H), 4.30(2H),4.99-5.03(1H), 5.43(1H), 5.42-5.48(1H), 5.68-5.82(1H), 7.06-7.60(6H)

Mass spectra (EI, m/z): 445(M⁺), 261, 233, 210, 184, 115, 73, 57

Example 2 Synthesis ofdimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride [Complex 1]

A 1.56 M solution of n-butyllithium in hexane (3.74 mL, 2.41 mmol) wasadded dropwise to a solution of(2-allyloxy-3-tert-butyl-5-methylphenyl)(3-[pyrrolidin-1-yl]-1H-inden-1-yl)dimethylsilane(0.74 g, 1.66 mmol) and triethylamine (1.05 g, 7.47 mmol) in toluene(7.4 mL) at −78° C. and stirred for 10 minutes and then at roomtemperature for 1 hour. A solution of titanium tetrachloride (0.47 g,2.49 mmol) in toluene (3.0 mL) was added dropwise to the reactionmixture at −78° C. and the resulting reaction mixture was warmed to 90°C. and then stirred for 3 hours. After insoluble substances were removedby filtration and the solvent was distilled off, the residue was washedwith hexane (1.3 mL) to obtaindimethylsilyl(3-[pyrrolidin-1-yl]-inden-1-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (0.66 g, 75.9%) as a brown solid.

¹H-NMR (deuterated benzene, δ(ppm)): 0.59(3H), 0.63(3H), 1.38-1.41(4H),1.53(9H), 2.29(3H), 3.30-3.40(4H), 5.48(1H), 6.97-7.77(6H)

Mass spectra (FD, m/z): 521(M⁺), 454, 403, 296, 295, 185, 184

Example 3 Synthesis of(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane

A solution of(2-allyloxy-3-tert-buyl-5-methylphenyl)chlorodimethylsilane (0.83 g,2.80 mmol) in toluene (2 mL) was added dropwise to a solution of(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)lithium (0.50 g,2.94 mmol) in tetrahydrofuran (20 mL) at −78° C. The resulting reactionmixture was warmed to room temperature and stirred for 1.5 hours. Afterthe solvent was distilled off under reduced pressure, toluene was addedand the mixture was filtered to remove insoluble substances. Thefiltrate was concentrated under reduced pressure to quantitativelyobtain(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane.

¹H-NMR (deuterated benzene, δ(ppm)): 0.24(s, 3H), 0.35(s, 3H), 1.49(s,9H), 1.86(s, 3H), 1.99(s, 3H), 2.20(s, 3H), 2.26(s, 3H), 3.92(s, 1H),4.34(s, 2H), 5.07-5.10(m, 1H), 5.49-5.55(m, 1H), 5.74-5.86(m, 1H),6.57(s, 1H), 7.16(s, 1H), 7.28(s, 1H)

Mass spectra (EI, m/z): 424 (M⁺), 367, 327, 221, 203, 187, 174, 161,128, 59, 44

Example 4 Synthesis ofdimethylsilyl(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride [Complex 2]

A 1.58 M solution of n-butyllithium in hexane (2.21 mL, 3.49 mmol) wasadded dropwise to a solution of(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)dimethylsilane(0.66 g, 1.55 mmol) and triethylamine (0.71 g, 6.98 mmol) in toluene(7.0 mL) at −78° C. and stirred for 10 minutes and then at roomtemperature for 2 hours. A solution of titanium tetrachloride (0.44 g,2.33 mmol) in toluene (4.5 mL) was added dropwise to the reactionmixture at −78° C. and stirred at room temperature for 5 hours. Thereaction mixture was concentrated and then filtered using hexane toremove insoluble substances. After the solvent was distilled off underreduced pressure, the residue was washed with pentane to obtaindimethylsilyl(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (0.07 g, 9.2%) as an orange solid.

¹H-NMR (deuterated benzene, δ(ppm)): 0.45(s, 3H), 0.55(s, 3H), 1.53(s,9H), 1.90(s, 3H), 2.04(s, 3H), 2.24(s, 3H), 2.29(s, 3H), 6.35(s, 1H),7.18(s, 1H), 7.24(s, 1H)

Mass spectra (EI, m/z): 500 (M⁺), 484, 449, 433

Example 5 Synthesis of(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)diethylsilane

A solution of (2-allyloxy-3-tert-buyl-5-methylphenyl)chlorodiethylsilane(0.91 g, 2.80 mmol) in toluene (2 mL) was added dropwise to a solutionof (2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)lithium (0.50g, 2.94 mmol) in tetrahydrofuran (20 mL) at −78° C. The resultingreaction mixture was warmed to room temperature and stirred for 5 hours.After the solvent was distilled off under reduced pressure, toluene wasadded and the mixture was filtered to remove insoluble substances. Thefiltrate was concentrated under reduced pressure to quantitativelyobtain(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)diethylsilane.

¹H-NMR (deuterated benzene, δ(ppm)): 0.81-1.08(m, 10H), 1.49(s, 9H),1.93(s, 3H), 1.99(s, 3H), 2.21(s, 3H), 2.27(s, 3H), 4.02(s, 1H),4.33-4.40(m, 2H), 5.05-5.11(m, 1H), 5.55-5.58(m, 1H), 5.73-5.89(m, 1H),6.56(s, 1H), 7.19(s, 1H), 7.28(s, 1H)

Mass spectra (EI, m/z): 452(M⁺), 423, 367, 288, 204, 189, 175, 161, 147,75, 57, 44

Example 6 Synthesis ofdiethylsilyl(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride [Complex 3]

A 1.57 M solution of n-butyllithium in hexane (3.30 mL, 5.18 mmol) wasadded dropwise to a solution of(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)diethylsilane(1.04 g, 2.30 mmol) and triethylamine (1.05 g, 10.35 mmol) in toluene(10.0 mL) at −78° C. and stirred for 10 minutes and then at roomtemperature for 3.5 hours. A solution of titanium tetrachloride (0.66 g,3.45 mmol) in toluene (6.9 mL) was added dropwise to the reactionmixture at −78° C. and stirred at room temperature for 5 hours. Afterthe reaction mixture was concentrated and filtered using hexane toremove insoluble substances, the solvent distilled off under reducedpressure. The residue was washed with pentane to obtaindiethylsilyl(2,4,5-trimethyl-6-hydrocyclopenta[2,3-b]thiophen-6-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (0.13 g, 10.9%) as an orange solid.

¹H-NMR (deuterated benzene, δ(ppm)): 0.80-1.03(m, 6H), 1.03-1.30(m, 4H),1.53(s, 9H), 1.97(s, 3H), 2.02(s, 3H), 2.24(s, 3H), 2.30(s, 3H), 6.36(s,1H), 7.19(s, 1H), 7.26(s, 1H)

Mass spectra (EI, m/z): 528 (M⁺), 499, 477

Example 7 Synthesis of(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane

A solution of(2-allyloxy-3-tert-buyl-5-methylphenyl)chlorodimethylsilane (0.71 g,2.40 mmol) in toluene (4 mL) was added dropwise to a solution of(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)lithium (0.51 g,2.40 mmol) in tetrahydrofuran (10 mL) at −78° C. The resulting reactionmixture was warmed to room temperature and stirred for 5 hours. Afterthe solvent was distilled off under reduced pressure, hexane was addedand the mixture was filtered to remove insoluble substances. Thefiltrate was concentrated under reduced pressure to quantitativelyobtain(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane.

¹H-NMR (deuterated benzene, δ(ppm)): 0.28(s 6H), 1.53(s, 9H), 2.21(s,3H), 2.23(s, 6H), 4.30-4.35(m, 2H), 4.43(s, 1H), 4.99-5.03(m, 1H),5.46-5.57(m, 1H), 5.63-5.79(m, 1H), 6.75(s, 2H), 7.18(s, 1H), 7.32(s,1H)

Mass spectra (EI, m/z): 466(M⁺), 261, 233, 205, 73, 57

Example 8 Synthesis ofdimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride [Complex 4]

A 1.56 M solution of n-butyllithium in hexane (1.50 mL, 2.34 mmol) wasadded dropwise to a solution of(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)dimethylsilane(0.45 g, 0.96 mmol) and triethylamine (0.47 g, 4.68 mmol) in toluene(5.0 mL) at −78° C. and stirred for 10 minutes and then at roomtemperature for 2 hours. A solution of titanium tetrachloride (0.27 g,1.44 mmol) in toluene (1.5 mL) was added dropwise to the reactionmixture at −78° C. and stirred at room temperature for 5 hours. Afterthe reaction mixture was concentrated and filtered using hexane toremove insoluble substances, the solvent was distilled off under reducedpressure. The residue was washed with pentane to obtaindimethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (35.4 mg, 6.8%) as a brown solid.

¹H-NMR (deuterated benzene, δ(ppm)): 0.61(s, 6H), 1.49(s, 9H), 2.05(s,3H), 2.06(s, 3H), 2.24(s, 3H), 6.67(s, 2H), 7.21(s, 1H), 7.26(s, 1H)

Mass spectra (EI, m/z): 524 (M⁺), 491, 287, 205, 75, 57

Example 9 Synthesis of(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)diethylsilane

At −78° C., n-butyllithium (1.56 M, 1.69 mL, 2.64 mmol) was addeddropwise to a solution of 2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen(0.50 g, 2.42 mmol) in tetrahydrofuran (10 mL) and the mixture wasstirred at room temperature for 4 hours. After the reaction mixture wascooled to −78° C., a solution of(2-allyloxy-3-tert-buyl-5-methylphenyl)chlorodiethylsilane (0.72 g, 2.20mmol) in toluene (3 mL) was added dropwise thereto. The resultingreaction mixture was warmed to room temperature and stirred for 2 hours.After the solvent was distilled off under reduced pressure, toluene wasadded and the mixture was filtered to remove insoluble substances. Thefiltrate was concentrated under reduced pressure to quantitativelyobtain(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)diethylsilane.

¹H-NMR (deuterated benzene, δ(ppm)): 0.74-0.92(m, 6H), 0.92-1.07(m, 4H),1.52(s, 9H), 2.24(s, 6H), 2.25(s, 3H), 4.32-4.40(m, 2H), 4.48(s, 1H),4.98-5.07(m, 1H), 5.48-5.58(m, 1H), 5.68-5.80(m, 1H), 6.75(s, 2H),7.26(s, 1H), 7.34(s, 1H)

Mass spectra (EI, m/z): 494 (M⁺), 289, 261, 233, 205, 73, 57

Example 10 Synthesis ofdiethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride [Complex 5]

A 1.56 M solution of n-butyllithium in hexane (1.77 mL, 2.77 mmol) wasadded dropwise to a solution of(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)diethylsilane(0.61 g, 1.23 mmol) and triethylamine (0.56 g, 5.54 mmol) in toluene(7.0 mL) at −78° C. and stirred for 10 minutes and then at roomtemperature for 2 hours. A solution of titanium tetrachloride (0.35 g,1.85 mmol) in toluene (3 mL) was added dropwise to the reaction mixtureat −78° C. and stirred at room temperature for 5 hours. After thereaction mixture was concentrated and filtered using hexane to removeinsoluble substances, the solvent was distilled off under reducedpressure. The residue was washed with pentane to obtaindiethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (71.0 mg, 10.1%) as a brown solid.

¹H-NMR (deuterated benzene, δ(ppm)): 1.01-1.07(m, 6H), 1.14-1.28(m, 4H),1.49(s, 9H), 2.04(s, 6H), 2.24(s, 3H), 6.67(s, 2H), 7.25(s, 1H), 7.28(s,1H)

Mass spectra (EI, m/z): 570 (M⁺), 541, 519

Example 11 Synthesis of(2-dimethylamino-4,5-dimethylcyclopentadienyl)(2-allyloxy-3-tert-butyl-5-methylphenyl)dimethylsilane

Under nitrogen atmosphere, after a solution of3,4-dimethylcyclopentenone (15.0 mmol) in toluene (10.0 mL) was cooledto −78° C., a solution of tetrakisdimethylaminotitanium (7.8 mmol) intoluene (8.3 mL) was added dropwise and the mixture was stirred at roomtemperature. After disappearance of ketone from the reaction mixture wasconfirmed by gas chromatography, the solvent was distilled off underreduced pressure. Hexane (18.3 mL) was added and a precipitated solidwas separated by filtration. The filtrate was concentrated to obtain1-dimethylamino-3,4-dimethylcyclopentadiene (2.23 g) as an oil. The oilwas added to hexane (30.0 mL) without being purified and cooled to −78°C. A 1.59 M solution of n-butyl lithium in hexane (15.0 mmol) was addeddropwise. The mixture was warmed to room temperature and stirred for 4hours. A formed solid was separated by filtration and dried to obtain1-dimethylamino-3,4-dimethylcyclopentadienyllithium (0.63 g, 29.6%) asflesh powder.

¹H-NMR (deuterated chloroform, δ(ppm)): 1.86(3H), 1.90(3H), 2.41(6H),2.66(2H), 4.94(1H)

Mass spectra (EI, m/z): 137 (M⁺), 122, 77

A solution of(2-allyloxy-3-tert-butyl-5-methylphenyl)dimethylchlorosilane (7.0 mmol)in toluene (12.1 mL) was added dropwise to a solution of1-dimethylamino-3,4-dimethylcyclopentadienyllithium (7.0 mmol) intetrahydrofuran (10.5 mL) and the mixture was stirred at roomtemperature for 6 hours. After the solvent was distilled off underreduced pressure, dehydrated pentane was added and a precipitated solidwas filtered off. The filtrate was concentrated to obtain the titlecompound (2.86 g, 100%) as an oil.

¹H-NMR (deuterated benzene, δ(ppm)): 0.36(3H), 0.59(3H), 1.71(9H),1.90(3H), 2.21(3H), 2.44(6H), 3.67(1H), 4.40-4.47(2H), 5.10-5.14(1H),5.27(1H), 5.54-5.60(1H), 5.79-5.88(1H), 7.24(1H), 7.28(1H)

Mass spectra (EI, m/z): 397 (M⁺), 382, 340, 261, 136

Example 12 Synthesis ofdimethylsilyl(2-dimethylamino-4,5-dimethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride [Complex 6]

A 1.56 M solution of n-butyllithium in hexane (8.0 mmol) was addeddropwise to a solution of(2-dimethylamino-4,5-dimethylcyclopentadienyl)(2-allyloxy-3-tert-butyl-5-methylphenyl)dimethylsilane(2.0 mmol) and triethylamine (16.0 mmol) in toluene (15.6 mL) at −78° C.and the mixture was warmed to room temperature and then stirred for 1hour. The reaction mixture was added dropwise to a solution of titaniumtetrachloride (6.0 mmol) in toluene (10.1 mL) at −78° C. The resultingreaction mixture was stirred at room temperature for 5 hours to obtain ared solution. The solvent of the solution was replaced with hexane and aprecipitated solid was filtered off. The filtrate was concentrated toobtain an oil, which was recrystallized from pentane to obtain the titlecompound (32.6 mg, 3.4%) as a black solid.

¹H-NMR (deuterated benzene, δ(ppm)): 0.45(3H), 0.52(3H), 1.57(9H),1.82(3H), 2.14(3H), 2.25(3H), 2.38(6H), 5.90(1H), 7.16(1H), 7.29(1H)

Mass spectra (EI, m/z): 397 (M⁺), 382, 340, 261, 136

<<Homopolymerization of Ethylene>>

Example 13

<Polymerization Condition A-1>

An autoclave was charged with toluene (5.0 mL) under nitrogen atmosphereand the temperature was stabilized at 40° C. It was then charged withethylene until it was pressurized to 0.60 MPa, and the pressure wasstabilized. Thereto MMAO (5.8 wt % Al, Tosoh-Akzo Corporation) (100μmol) and the Complex 2 (0.10 μmol) were added to carry outpolymerization for 30 min. As a result of polymerization, a polymer wasproduced in an amount of 9.2×10⁶ g per 1 mol of titanium and per anhour.

Example 14

<Polymerization Condition B-1>

Polymerization was carried out in the same manner as Example 13, exceptthat a solution of triisobutylaluminum in hexane (40 μL, 1.0 M, KantoChemical Co., Ltd.) and pentafluorophenylborane (0.30 μmol) were used inplace of MMAO. As a result of polymerization, a polymer was produced inan amount of 1.6×10⁶ g per 1 mol of titanium and per an hour.

Example 15

<Polymerization Condition C-1>

Polymerization was carried out in the same manner as Example 13, exceptthat a solution of triisobutylaluminum in hexane (40 μL, 1.0 M, KantoChemical Co., Ltd.) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. As a result of polymerization, a polymer was produced in an amountof 11.4×10⁶ g per 1 mol of titanium and per an hour.

Example 16

<Polymerization Condition D-1>

Polymerization was carried out in the same manner as Example 13, exceptthat a solution of triisobutylaluminum in hexane (40 μL, 1.0 M, KantoChemical Co., Ltd.) and triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) were used in place ofMMAO. As a result of polymerization, a polymer was produced in an amountof 5.2×10⁶ g per 1 mol of titanium and per an hour.

<<Copolymerization of Ethylene/1-Hexene>>

Example 17

<Polymerization Condition A-2>

An autoclave was charged with toluene (5.0 mL) and 1-hexene (50 μL)under nitrogen atmosphere and the temperature was stabilized at 40° C.It was then charged with ethylene until it was pressurized to 0.60 MPa,and the pressure was stabilized. Thereto MMAO (5.8 wt % Al, Tosoh-AkzoCorporation) (100 μmol) and the Complex 2 (0.10 μmol) were added tocarry out polymerization for 30 min. As a result of polymerization, apolymer having the molecular weight (Mw)=739,000, the molecular weightdistribution (Mw/Mn)=2.0, Tm=102.8° C. and SCB=6 was produced in anamount of 7.0×10⁶ g per 1 mol of titanium and per an hour.

Example 18

<Polymerization Condition A-3>

Polymerization was carried out in the same manner as Example 17, exceptthat the polymerization temperature was 70° C. As a result ofpolymerization, a polymer having the molecular weight (Mw)=222,000, themolecular weight distribution (Mw/Mn)=1.8, Tm=98.7° C. and SCB=7 wasproduced in an amount of 40.9×10⁶ g per 1 mol of titanium and per anhour.

Example 19

<Polymerization Condition B-2>

An autoclave was charged with toluene (5.0 mL) and 1-hexene (50 μL)under nitrogen atmosphere and the temperature was stabilized at 40° C.It was then charged with ethylene until it was pressurized to 0.60 MPa,and the pressure was stabilized. Thereto a solution oftriisobutylaluminum in hexane (40 μL, 1.0 M, Kanto Chemical Co., Ltd.),pentafluorophenylborane (0.30 μmol) and the Complex 2 (0.10 μmol) wereadded to carry out polymerization for 30 min. As a result ofpolymerization, a polymer having the molecular weight (Mw)=904,000, themolecular weight distribution (Mw/Mn)=1.7 and Tm=100.2° C. was producedin an amount of 1.1×10⁶ g per 1 mol of titanium and per an hour.

Example 20

<Polymerization Condition B-3>

Polymerization was carried out in the same manner as Example 19, exceptthat the polymerization temperature was 70° C. As a result ofpolymerization, a polymer having the molecular weight (Mw)=575,000, themolecular weight distribution (Mw/Mn)=1.7, Tm=103.9° C. and SCB=24 wasproduced in an amount of 2.1×10⁶ g per 1 mol of titanium and per anhour.

Example 21

<Polymerization Condition C-2>

An autoclave was charged with toluene (5.0 mL) and 1-hexene (50 μL)under nitrogen atmosphere and the temperature was stabilized at 40° C.It was then charged with ethylene until it was pressurized to 0.60 MPa,and the pressure was stabilized. Thereto a solution oftriisobutylaluminum in hexane (40 μL, 1.0 M, Kanto Chemical Co., Ltd.),dimethylanilinium tetrakis(pentafluorophenyl)borate (0.30 μmol) and theComplex 2 (0.10 μmol) were added to carry out polymerization for 30 min.As a result of polymerization, a polymer having the molecular weight(Mw)=1,048,000, the molecular weight distribution (Mw/Mn)=2.7, Tm=114.3°C. and SCB=16 was produced in an amount of 129.5×10⁶ g per 1 mol oftitanium and per an hour.

Example 22

<Polymerization Condition C-3>

Polymerization was carried out in the same manner as Example 21, exceptthat the polymerization temperature was 70° C. As a result ofpolymerization, a polymer having the molecular weight (Mw)=648,000, themolecular weight distribution (Mw/Mn)=2.0, Tm=108.4° C. and SCB=18 wasproduced in an amount of 74.3×10⁶ g per 1 mol of titanium and per anhour.

Example 23

<Polymerization Condition C-4>

Polymerization was carried out in the same manner as Example 21, exceptthat the polymerization temperature was 130° C. and 4 μL of the solutionof triisobutylaluminum in hexane was used. As a result ofpolymerization, a polymer having the molecular weight (Mw)=250,000, themolecular weight distribution (Mw/Mn)=2.2, Tm=104.3° C. and SCB=24 wasproduced in an amount of 3.2×10⁶ g per 1 mol of titanium and per anhour.

Example 24

<Polymerization Condition D-2>

An autoclave was charged with toluene (5.0 mL) and 1-hexene (50 μL)under nitrogen atmosphere and the temperature was stabilized at 40° C.It was then charged with ethylene until it was pressurized to 0.60 MPa,and the pressure was stabilized. Thereto a solution oftriisobutylaluminum in hexane (40 μL, 1.0 M, Kanto Chemical Co., Ltd.),triphenylmethyl tetrakis(pentafluorophenyl)borate (0.30 μmol) and theComplex 2 (0.10 μmol) were added to carry out polymerization for 30 min.As a result of polymerization, a polymer having the molecular weight(Mw)=1,104,000, the molecular weight distribution (Mw/Mn)=3.1, Tm=118.8°C. and SCB=14 was produced in an amount of 56.6×10⁶ g per 1 mol oftitanium and per an hour.

Example 25

<Polymerization Condition D-3>

Polymerization was carried out in the same manner as Example 24, exceptthat the polymerization temperature was 70° C. As a result ofpolymerization, a polymer having the molecular weight (Mw)=767,000, themolecular weight distribution (Mw/Mn)=2.8, Tm=107.3° C. and SCB=23 wasproduced in an amount of 77.4×10⁶ g per 1 mol of titanium and per anhour.

Example 26

<Polymerization Condition D-4>

Polymerization was carried out in the same manner as Example 24, exceptthat the polymerization temperature was 130° C. and 4 μL of the solutionof triisobutylaluminum in hexane was used. As a result ofpolymerization, a polymer having the molecular weight (Mw)=282,000, themolecular weight distribution (Mw/Mn)=3.1, Tm=101.5° C. and SCB=30 wasproduced in an amount of 56.6×10⁶ g per 1 mol of titanium and per anhour.

Example 27

<Polymerization Condition A-5>

Polymerization was carried out in the same manner as Example 17, exceptthat 60 μL of 1-hexene was charged and the Complex 5 was used. As aresult of polymerization, a polymer having the molecular weight(Mw)=744,000, the molecular weight distribution (Mw/Mn)=2.1, Tm=93.5° C.and SCB=14 was produced in an amount of 14.4×10⁶ g per 1 mol of titaniumand per an hour.

Example 28

<Polymerization Condition B-5>

Polymerization was carried out in the same manner as Example 19, exceptthat 60 μL of 1-hexene was charged and the Complex 4 was used. As aresult of polymerization, a polymer having the molecular weight(Mw)=903,000, the molecular weight distribution (Mw/Mn)=1.5 and Tm=89.1°C. was produced in an amount of 1.7×10⁶ g per 1 mol of titanium and peran hour.

Example 29

<Polymerization Condition C-5>

Polymerization was carried out in the same manner as Example 21, exceptthat 60 μL of 1-hexene was charged and the Complex 4 was used. As aresult of polymerization, a polymer having the molecular weight(Mw)=988,000, the molecular weight distribution (Mw/Mn)=2.1, Tm=112.4°C. and SCB=32 was produced in an amount of 113.2×10⁶ g per 1 mol oftitanium and per an hour.

Example 30

<Polymerization Condition C-6>

Polymerization was carried out in the same manner as Example 23, exceptthat 40 μL of 1-hexene was charged and the Complex 4 was used. As aresult of polymerization, a polymer having the molecular weight(Mw)=272,000, the molecular weight distribution (Mw/Mn)=2.1, Tm=101.2°C. and SCB=30 was produced in an amount of 26.7×10⁶ g per 1 mol oftitanium and per an hour.

Example 31

<Polymerization Condition D-5>

Polymerization was carried out in the same manner as Example 24, exceptthat 60 μL of 1-hexene was charged and the Complex 4 was used. As aresult of polymerization, a polymer having the molecular weight(Mw)=408,000, the molecular weight distribution (Mw/Mn)=1.9, Tm=109.8°C. and SCB=18 was produced in an amount of 41.3×10⁶ g per 1 mol oftitanium and per an hour.

Example 32

<Polymerization Condition D-6>

Polymerization was carried out in the same manner as Example 26, exceptthat 40 μL of 1-hexene was charged and the Complex 4 was used. As aresult of polymerization, a polymer having the molecular weight(Mw)=255,000, the molecular weight distribution (Mw/Mn)=2.0, Tm=102.4°C. and SCB=24 was produced in an amount of 7.0×10⁶ g per 1 mol oftitanium and per an hour.

The following tables 1 to 5 show the catalytic components,polymerization conditions, catalytic activity and reaction results ofExamples 13 to 91 and those in Comparative Examples 1 to 9 usingdimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride [Complex 7].

TABLE 1 Ethylene Hhomopolymerization [Complex 7]

Example Complex Polymerization condition Activity*¹ 33 1 A-1 0.6 34 1B-1 0.3 35 1 C-1 3.4 36 1 D-1 4.0 13 2 A-1 9.2 14 2 B-1 1.6 15 2 C-111.4 16 2 D-1 5.2 37 3 A-1 8.6 38 3 B-1 4.7 39 3 C-1 59.5 40 3 D-1 4.541 4 A-1 1.9 42 4 B-1 1.9 43 4 C-1 55.0 44 4 D-1 10.2 45 5 A-1 11.3 46 5B-1 3.3 47 5 C-1 37.4 48 5 D-1 5.4 49 6 A-1 1.3 50 6 B-1 2.8 51 6 C-15.3 52 6 D-1 5.0 *¹(x10⁶ gPE/mol-cat/hr)

TABLE 2 Ethylene/1-Hexene Copolymerization (MMAO) PolymerizationTemperature Complex condition (° C.) Activity*¹ Mw Mw/Mn Tm(° C.) SCB*²Example 17 2 A-2 40 7.0 739,000 2.0 102.8 6 18 2 A-3 70 40.9 222,000 1.898.7 7 53 3 A-2 40 6.3 651,000 2.0 105.8 4 54 3 A-3 70 39.7 164,000 2.2101.8 15 55 4 A-3 70 91.4 197,000 1.8 95.8 20 27 5 A-5 40 14.4 744,0002.1 93.5 14 56 5 A-3 70 76.5 226,000 2.0 97.8 14 57 6 A-5 40 1.5 532,0002.0 109.0 6 58 6 A-3 70 1.6 144,000 1.6 113.0 9 Comparative Example  1 7A-3 70 14.3 128,000 3.2 91.1 23 *¹(×10⁶ gPE/mol-cat/hr) *²The number ofbranched methyl groups per 1,000 carbon atoms of a polymer.

TABLE 3 Ethylene/1-Hexene Copolymerization (TIBA/B(C₆F₅)₃)Polymerization Temperature Complex condition (° C.) Activity*¹ Mw Mw/MnTm(° C.) SCB*² Example 19 2 B-2 40 1.1 904,000 1.7 100.2 ND 20 2 B-3 702.1 575,000 1.7 103.9 24 59 3 B-2 40 2.3 733,000 1.9 105.4 11 60 3 B-370 2.2 439,000 1.8 98.6 ND 28 4 B-5 40 1.7 903,000 1.5 89.1 ND 61 4 B-370 2.1 360,000 1.5 91.9 ND 62 5 B-5 40 12.4 1,046,000 1.7 87.5 20 63 5B-3 70 2.3 499,000 1.5 83.2 15 64 6 B-5 40 2.6 1,341,000 1.5 105.5  8 656 B-3 70 1.0 510,000 1.5 104.4  7 Comparative Example  2 7 B-2 40 1.2566,000 2.8 85.6 24  3 7 B-3 70 1.0 333,000 2.2 83.7 19 *¹(×10⁶gPE/mol-cat/hr) *²The number of branched methyl groups per 1,000 carbonatoms of a polymer. ND: undone

TABLE 4 Ethylene/1-Hexene Copolymerization (TIBA/AB) PolymerizationTemperature Complex condition (° C.) Activity*¹ Mw Mw/Mn Tm(° C.) SCB*²Example 66 1 C-2 40 6.9 556,000 2.7 101.3 8 67 1 C-3 70 48.1 289,000 2.8102.8 9 68 1 C-4 130 45.3 379,000 3.0 105.9 12 21 2 C-2 40 129.51,048,000 2.7 114.3 16 22 2 C-3 70 74.3 648,000 2.0 108.4 18 23 2 C-4130 3.2 250,000 2.2 104.3 24 69 3 C-2 40 282.1 987,000 2.7 110.9 12 70 3C-3 70 32.2 758,000 5.1 112.6 33 71 3 C-4 130 31.8 228,000 3.5 104.2 2729 4 C-5 40 113.2 988,000 2.1 112.4 32 72 4 C-3 70 58.1 323,000 1.9109.2 40 30 4 C-6 130 26.7 272,000 2.1 101.2 30 73 5 C-5 40 49.2 913,0002.1 109.5 23 74 5 C-3 70 20.4 812,000 1.8 127.6 15 75 5 C-6 130 27.5268,000 2.0 99.3 23 76 6 C-5 40 4.9 936,000 2.2 101.5 14 77 6 C-3 70 8.6547,000 1.8 105.2 10 78 6 C-6 130 10.1 360,000 1.6 103.5 6 ComparativeExample  4 7 C-2 40 26.3 654,000 2.6 98.2 19  5 7 C-3 70 152.3 260,0002.5 88.0 28  6 7 C-4 130 30.8 169,000 2.1 90.3 24 *¹(×10⁶gPE/mol-cat/hr) *²The number of branched methyl groups per 1,000 carbonatoms of a polymer.

TABLE 5 Ethylene/1-Hexene Copolymerization (TIBA/CB) PolymerizationTemperature Complex condition (° C.) Activity*¹ Mw Mw/Mn Tm(° C.) SCB*²Example 79 1 D-2 40 9.4 522,000 2.2 100.9 10 80 1 D-3 70 24.1 362,0002.6 104.1 11 81 1 D-4 130 13.6 380,000 2.8 107.3 12 24 2 D-2 40 56.61,104,000 3.1 118.8 14 25 2 D-3 70 77.4 767,000 2.8 107.3 23 26 2 D-4130 2.3 282,000 3.1 101.5 30 82 3 D-2 40 303.0 923,000 2.3 112.5 17 83 3D-3 70 20.1 679,000 5.2 108.1 21 84 3 D-4 130 10.0 229,000 4.1 103.5 2931 4 D-5 40 41.3 408,000 1.9 109.8 18 85 4 D-3 70 76.3 348,000 1.8 118.641 32 4 D-6 130 7.0 255,000 2.0 102.4 24 86 5 D-5 40 223.9 909,000 2.0130.1 11 87 5 D-3 70 19.6 481,000 2.0 112.2 17 88 5 D-6 130 9.1 301,0002.4 98.8 24 89 6 D-5 40 15.5 615,000 2.2 105.4 17 90 6 D-3 70 13.4514,000 1.8 105.2 8 91 6 D-6 130 8.7 409,000 1.6 106.3 6 ComparativeExample  7 7 D-2 40 59.1 535,000 6.7 112.7 17  8 7 D-3 70 75.3 357,0003.6 118.0 12  9 7 D-4 130 9.5 189,000 2.7 89.4 28 *¹(×10⁶gPE/mol-cat/hr). *²The number of branched methyl groups per 1,000 carbonatoms of a polymer.

Example 92 Synthesis of ethyl(2Z)-2-methyl-3-[5-methylthiophen-2-yl]-2-propenoate

Under nitrogen atmosphere, a reactor was loaded with 60% sodium hydride(87.1 g, 2.15 mol) and dry THF (130 mL). A solution of triethyl2-phosphonopropionate (239 mL, 1.54 mol) in dry THF (160 mL) was addeddropwise into the reactor in an ice bath. The mixture was stirred atroom temperature for 1.5 hours, and successively, in an ice bath, asolution of 5-methylthiophene-2-carboxyaldehyde (180.0 g, 1.43 mol) indry THF (430 mL) was added dropwise thereto under ice bath cooling andstirred at room temperature for 5 hours. An aqueous saturated ammoniumchloride solution was added to the resulting reaction mixture and themixture was extracted with diethyl ether to obtain an organic layer. Theorganic layer was washed with a saturated brine and dried over magnesiumsulfate anhydride. The solvent was distilled off under reduced pressureto obtain ethyl (2Z)-2-methyl-3-[5-methylthiophen-2-yl]-2-propenoate(291.8 g, 97.0%) as a dark red liquid.

Example 93 Synthesis of methyl2-methyl-3-[5-methylthiophen-2-yl]-2-propanoate

Under nitrogen atmosphere, a reactor was loaded with ethyl(2Z)-2-methyl-3-[5-methylthiophen-2-yl]-2-propenoate (20.0 g, 95.1 mmol)and dry methanol (100 mL) and magnesium (7.0 g, 289.0 mmol) was added insmall portions and gradually thereto. The mixture was stirred for 5hours, acidified by addition of an aqueous 3N hydrochloric acid solutionand then extracted with ethyl acetate to obtain an organic layer. Theorganic layer was washed with saturated brine and dried over anhydrousmagnesium sulfate. The solvent was distilled off under reduced pressureto obtain a dark red liquid. The liquid was purified by silica gelchromatography (hexane/ethyl acetate=10/1) to obtain methyl2-methyl-3-[5-methylthiophen-2-yl]-2-propanoate (11.2 g, 59.4%) as apale yellow liquid.

Example 94 Synthesis of 2-methyl-3-[5-methylthiophen-2-yl]-2-propanoicacid

Under nitrogen atmosphere, a reactor was loaded with methyl2-methyl-3-[5-methylthiophen-2-yl]-2-propanoate (162.9 g, 0.82 mmol) andClaisen reagent*(391 mL) and the mixture was stirred at room temperaturefor 1 hour. The reaction mixture was adjusted to pH 1-2 by addition ofan aqueous 6N hydrochloric acid solution and then extracted with ethylacetate to obtain an organic layer. The organic layer was washed withsaturated brine and dried over anhydrous magnesium sulfate. The solventwas distilled off under reduced pressure to obtain2-methyl-3-[5-methylthiophen-2-yl]-2-propanoic acid (149.6 g, 99.0%) asa pale yellow oil.

*Claisen reagent: a solution of potassium hydroxide (35 g) in a mixedsolvent of water (25 mL) and methanol 100 mL)

Example 95 Synthesis of2,5-dimethyl-5,6-dihydrocyclopenta[1,2-b]thiophen-4-one

Under nitrogen atmosphere, a reactor was loaded with polyphosphoric acid(72.1 g) and phosphorus pentoxide (72.1 g, 0.51 mol) was added theretoand stirred at 140° C. for 1 hour. Then, a solution of2-methyl-3-[5-methylthiophen-2-yl]propanoic acid (43.0 g, 0.23 mol) in1,2-dichloroethane (75 mL) was added dropwise and stirred at 100° C. for2 hours. The reaction mixture was added to iced water (1,000 mL) withstirring and after 30 minutes, extracted with chloroform to obtain anorganic layer. The organic layer was washed with an aqueous saturatedsodium carbonate solution and dried over anhydrous magnesium sulfate.The solvent was distilled off under reduced pressure to obtain a blackoil. The oil was purified by silica gel chromatography (hexane/ethylacetate=5/1) to obtain2,5-dimethyl-5,6-dihydrocyclopenta[1,2-b]thiophen-4-one (32.6 g, 84.1%)as a reddish brown oil.

Example 96 Synthesis of2,4,5-trimethyl-6-hydrocyclopenta[1,2-b]thiophene

A solution of methyllithium in diethyl ether (1.04 M, Kanto ChemicalCo., Ltd.) (31.8 mL, 33.1 mmol) was added dropwise to a solution of2,5-dimethyl-5,6-dihydrocyclopenta[1,2-b]thiophen-4-one (5.00 g, 30.1mmol) in tetrahydrofuran (50 mL) at −78° C. and stirred at roomtemperature for 4 hours. After addition of an aqueous saturated ammoniumchloride solution, the mixture was extracted with ethyl acetate, washedwith saturated brine and then dried over sodium sulfate. The solvent wasconcentrated under reduced pressure to obtain2,4,5-trimethyl-4,5,6-trihydrocyclopenta[1,2-b]thiophen-4-ol (5.18 g,95%). The obtained2,4,5-trimethyl-4,5,6-trihydrocyclopenta[1,2-b]thiophen-4-ol wasdissolved in tetrahydrofuran (50 mL) and 3% hydrochloric acid (15 mL)was added at room temperature. The mixture was then stirred for 3 hours.The reaction mixture was separated by addition of toluene and water. Anorganic layer was washed with water and saturated brine and then driedover magnesium sulfate. The solvent was concentrated under reducedpressure to quantitatively obtain2,4,5-trimethyl-6-hydrocyclopenta[1,2-b]thiophene.

¹H-NMR (deuterated chloroform, δ(ppm)): 1.97(s, 3H), 1.98(s, 3H),2.50(s, 3H), 3.16(s, 2H), 6.58(s, 1H)

¹³C-NMR (deuterated chloroform, δ(ppm)): 12.23, 14.64, 16.62, 40, 83,116.94, 130.81, 136.38, 137.95, 142.32, 153.31.

Mass spectra (EI, m/z): 164 (M⁺), 149, 134, 115, 51, 39, 27

Example 97 Synthesis of 2,5-dimethyl-6-hydrocyclopenta[1,2-b]thiophene

Under nitrogen atmosphere, lithium aluminum hydride (5.80 g, 66.0 mmol)and dry diethyl ether (53 mL) were loaded and a solution of2,5-dimethyl-5,6-dihydrocyclopenta[1,2-b]thiophen-4-one (22.0 g, 132.2mmol) in dry tetrahydrofuran (44 mL) was added dropwise thereto in anice bath. The mixture was then stirred at room temperature for 3 hours.Then, an aqueous saturated ammonium chloride solution was added to thereaction mixture and it was extracted with ethyl acetate to obtain anorganic layer. The organic layer was washed with saturated brine anddried over anhydrous magnesium sulfate. The solvent was distilled offunder reduced pressure to obtain2,5-dimethyl-4,5,6-trihydrocyclopenta[1,2-b]thiophen-4-ol (22.5 g, 99%)as a pale yellow oil.

The obtained 2,5-dimethyl-4,5,6-trihydrocyclopenta[1,2-b]thiophen-4-ol(22.2 g, 66.0 mmol) and toluene (200 mL) were loaded, andp-toluenesulfonic acid monohydrate (804 mg) and molecular sieves 3A (10g) were added. The mixture was then stirred at 95 to 100° C. for 1 hour.Then, water was added to the reaction mixture and it was extracted withethyl acetate to obtain an organic layer. The organic layer was washedwith saturated brine and dried over anhydrous magnesium sulfate. Thesolvent was distilled off under reduced pressure to obtain a pale yellowoil (19.6 g). The oil was purified by silica gel column chromatography(hexane) to obtain 2,5-dimethyl-6-hydrocyclopenta[1,2-b]thiophene (15.6g, 79%) as a white solid.

¹H-NMR (deuterated chloroform, δ(ppm)): 1.82(s, 3H), 2.27(s, 3H),2.83(s, 2H), 6.28(s, 1H), 6.52(s, 1H)

¹³C-NMR (deuterated chloroform, δ(ppm)): 15.80, 16.75, 40, 12, 117.69,123.66, 137.67, 141.64, 145.80, 150.12

<<Propylene Homopolymerization>>

Example 98

<Polymerization Condition E-1>

An autoclave was charged with toluene (5.0 mL) under nitrogen atmosphereand the temperature was stabilized at 40° C. It was then charged withpropylene until it was pressurized to 0.20 MPa, and the pressure wasstabilized. Thereto MMAO (5.8% by weight of Al, Tosoh Akzo Corporation)(100 μmol) and the Complex 4 (0.10 μmol) were added to carry outpolymerization for 30 min. As a result of polymerization, a polymerhaving the molecular weight (Mw)=248,000, the molecular weightdistribution (Mw/Mn)=1.5 and Tm=116.6° C. was produced in an amount of1.9×10⁶ g per 1 mol of titanium and per an hour.

Example 99

<Polymerization Condition F-1>

An autoclave was charged with toluene (5.0 mL) under nitrogen atmosphereand the temperature was stabilized at 40° C. It was then charged withpropylene until it was pressurized to 0.20 MPa, and the pressure wasstabilized. Thereto a solution of triisobutylaluminum in hexane (40 μL,1.0 M, Kanto Chemical Co., Ltd.), pentafluorophenylborane (0.30 mmol)and the Complex 4 (0.10 μmol) were added to carry out polymerization for30 min. As a result of polymerization, a polymer was produced in anamount of 1.0×10⁵ g per 1 mol of titanium and per an hour.

Example 100

<Polymerization Condition G-1>

An autoclave was charged with toluene (5.0 mL) under nitrogen atmosphereand the temperature was stabilized at 40° C. It was then charged withpropylene until it was pressurized to 0.20 MPa, and the pressure wasstabilized. Thereto a solution of triisobutylaluminum in hexane (40 μL,1.0 M, Kanto Chemical Co., Ltd.), dimetylaniliniumtetrakis(pentafluorophenyl)borate (0.30 μmol) and the Complex 4 (0.10μmol) were added to carry out polymerization for 30 min. As a result ofpolymerization, a polymer having the molecular weight (Mw)=491,000, themolecular weight distribution (Mw/Mn)=1.7 and Tm=104.4° C. was producedin an amount of 16.9×10⁶ g per 1 mol of titanium and per an hour.

Example 101

<Polymerization Condition H-1>

An autoclave was charged with toluene (5.0 mL) under nitrogen atmosphereand the temperature was stabilized at 40° C. It was then charged withpropylene until it was pressurized to 0.20 MPa, and the pressure wasstabilized. Thereto a solution of triisobutylaluminum in hexane (40 μL,1.0 M, Kanto Chemical Co., Ltd.), triphenylmethyltetrakis(pentafluorophenyl)borate (0.30 μmol) and the Complex 4 (0.10μmol) were added to carry out polymerization for 30 min. As a result ofpolymerization, a polymer having the molecular weight (Mw)=527,000, themolecular weight distribution (Mw/Mn)=1.64 and Tm=113.4° C. was producedin an amount of 16.1×10⁶ g per 1 mol of titanium and per an hour.

<<Copolymerization of Ethylene/1-Butene>>

Example 102

<Polymerization Condition I-1>

After a flask was charged with toluene (1.0 L) under nitrogenatmosphere, ethylene (8.0 L/min) and 1-butene (2.0 L/min) were blownthereinto respectively and the temperature was stabilized at 30° C.Thereto a solution of triisobutylaluminum in hexane (0.5 mL, 1.0 M,Kanto Chemical Co., Ltd.), the Complex 4 (0.5 μmol) anddimethylanilinium tetrakis(pentafluorophenyl)borate (0.5 μmol) wereadded to carry out polymerization for 60 min. As a result ofpolymerization, a polymer having the molecular weight (Mw)=292,000 andthe molecular weight distribution (Mw/Mn)=1.43 was produced in an amountof 4.3×10⁶ g per 1 mol of titanium and per an hour.

Example 103

Polymerization was carried out in the same manner as Example 102, exceptthat the Complex 5 was used. As a result of polymerization, a polymerhaving the molecular weight (Mw)=15,000 and the molecular weightdistribution (Mw/Mn)=1.46 was produced in an amount of 10.5×10⁶ g per 1mol of titanium and per an hour.

<<Copolymerization of Propylene/1-Butene>>

Example 104

<Polymerization Condition J-1>

After a flask was charged with toluene (1.0 L) under nitrogenatmosphere, propylene (8.0 L/min) and 1-butene (2.0 L/min) were blownthereinto respectively and the temperature was stabilized at 30° C.Thereto a solution of triisobutylaluminum in hexane (0.5 mL, 1.0 M,Kanto Chemical Co., Ltd.), the Complex 4 (0.5 μmol) anddimethylanilinium tetrakis(pentafluorophenyl)borate (0.5 μmol) wereadded to carry out polymerization for 60 min. As a result ofpolymerization, a polymer having the molecular weight (Mw)=297,000 andthe molecular weight distribution (Mw/Mn)=1.47 was produced in an amountof 2.0×10⁶ g per 1 mol of titanium and per an hour.

Example 105

Polymerization was carried out in the same manner as Example 104, exceptthat the Complex 5 was used. As a result of polymerization, a polymerhaving the molecular weight (Mw)=763,000 and the molecular weightdistribution (Mw/Mn)=1.45 was produced in an amount of 4.5×10⁶ g per 1mol of titanium and per an hour.

<<Copolymerization of Ethylene/Styrene/Norbornene>>

Example 106

<Polymerization Condition K-1>

An autoclave was charged with toluene (100 mL), styrene (200 mmol) andnorbornene (200 mmol) under nitrogen atmosphere. The autoclave was thencharged with ethylene until it was pressurized to 0.4 MPa, and thetemperature was stabilized at 50° C. Thereto a solution oftriisobutylaluminum in hexane (1.0 mL, 1.0 M, Kanto Chemical Co., Ltd.),the Complex 4 (5.0 μmol) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (10.0 μmol) were added to carry outpolymerization for 60 min. As a result of polymerization, a polymer wasproduced in an amount of 5.3×10⁶ g per 1 mol of titanium and per anhour.

Example 107

<Polymerization Condition K-2>

An autoclave was charged with toluene (150 mL), styrene (300 mmol) andnorbornene (300 mmol) under nitrogen atmosphere. The autoclave was thencharged with ethylene until it was pressurized to 0.4 MPa, and thetemperature was stabilized at 50° C. Thereto a solution oftriisobutylaluminum in hexane (1.5 mL, 1.0 M, Kanto Chemical Co., Ltd.),the Complex 5 (7.5 μmol) and dimethylaniliniumtetrakis(pentafluorophenyl)borate (15.0 μmol) were added to carry outpolymerization for 60 min. As a result of polymerization, a polymer wasproduced in an amount of 5.0×10⁶ g per 1 mol of titanium and per anhour.

<<High Temperature and High Pressure Polymerization>>

Example 108

<Polymerization Condition L-1>

An autoclave was charged with cyclohexane (185 mL) and 1-hexene (15 mL)under nitrogen atmosphere and the temperature was stabilized at 180° C.It was then charged with ethylene until it was pressurized to 2.50 MPa,and the pressure was stabilized. Thereto triisobutylaluminum (0.30mmol), dimethylanilinium tetrakis(pentafluorophenyl)borate (3.0 μmol)and the Complex 5 (0.50 μmol) were added to carry out polymerization for2 min. As a result of polymerization, a polymer having the molecularweight (Mw)=113,500 and the molecular weight distribution (Mw/Mn)=1.8was produced in an amount of 21.5×10⁷ g per 1 mol of titanium and per anhour.

The following Table 6 shows the catalytic components, polymerizationconditions, catalytic activity, reaction results of Examples 108 to 111and those in Comparative Example 10 usingdimethylsilyl(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdimethoxide [Complex 8].

TABLE 6 Ethylene/1-hexene copolymerization (TIBA/AB) PolymerizationTemperature Complex condition (° C.) Activity*¹ Mw Mw/Mn SCB*² Example108 5 L-1 180 21.5 113,500 1.8 24.7 109 3 L-1 180 21.4 83,000 2.0 22.6110 2 L-1 180 24.1 74,700 1.8 20.3 111 1 L-1 180 8.2 88,500 1.7 11.8Comparative Example  10 8 L-1 180 13.1 52,600 2.1 34.5 *¹(×10⁷gPE/mol-cat/hr) *²The number of branched methyl groups per 1,000 carbonatoms of a polymer.

Example 112 Synthesis of(2-allyloxy-3-tert-butyl-5-methylphenyl)(cyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)diethylsilane

To a solution of cyclopenta[1,2-b:4,3-b′]dithiophene (0.50 g, 280 mmol)in tetrahydrofuran (25 mL) was added dropwise n-butyllithium (1.56 M,1.88 mL, 2.94 mmol) at −78° C. and stirred at room temperature for 4hours. The mixture was cooled to −78° C. and a solution of(2-allyloxy-3-tert-buyl-5-methylphenyl)chlorodimethylsilane (0.83 g,2.80 mmol) in toluene (5 mL) was added dropwise thereto. The resultingreaction mixture was warmed to room temperature and stirred for 2 hours.After the solvent was distilled off under reduced pressure, toluene wasadded and the mixture was filtered to remove insoluble substances. Thefiltrate was concentrated under reduced pressure to quantitativelyobtain(2-allyloxy-3-tert-butyl-5-methylphenyl)(cyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)diethylsilane.

¹H-NMR (deuterated benzene, δ(ppm)): 0.67-0.96(m, 10H), 1.51(s, 9H),2.23(s, 3H), 4.33-4.35(m, 2H), 4.49(s, 1H), 4.99-5.04(m, 1H),5.43-5.55(m, 1H), 5.67-5.78(m, 1H), 6.93(d, J=5.0 Hz, 2H), 7.03(d, J=5.0Hz, 2H), 7.20(s, 1H), 7.34 (s, 1H)

Example 113 Synthesis ofdiethylsilyl(2,5-dimethylcyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride [Complex 9]

A 1.56 M solution of n-butyllithium in hexane (3.78 mL, 5.9 mmol) wasadded dropwise to a solution of(2-allyloxy-3-tert-butyl-5-methylphenyl)(cyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)diethylsilane(1.23 g, 2.6 mmol) and triethylamine (1.20 g, 11.9 mmol) in toluene(15.0 mL) at −78° C. and stirred for 10 minutes and then at roomtemperature for 2 hours. A solution of titanium tetrachloride (0.75 g,4.0 mmol) in toluene (4.0 mL) was added dropwise at −78° C. to thereaction mixture and the mixture was stirred at room temperature for 5hours. The reaction mixture was concentrated and filtered using hexaneto remove insoluble substances. After the solvent was distilled offunder reduced pressure, the residue was washed with pentane to obtaindiethylsilyl(cyclopenta[1,2-b:4,3-b′]dithiophen-7-yl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride (137.5 mg, 9.6%) as a reddish brown solid.

¹H-NMR (deuterated benzene, δ(ppm)): 0.81-1.03(m, 6H), 1.16-1.27(m, 4H),1.46(s, 9H), 2.21(s, 3H), 6.80(d, J=5.5 Hz, 2H), 6.91(d, J=5.5 Hz, 2H),7.22(s, 1H), 7.25(s, 1H).

Mass spectra (EI, m/z): 542 (M⁺), 513, 491, 275

INDUSTRIAL APPLICABILITY

High molecular weight polyolefin can be produced with high catalyticactivity by using a transition metal complex obtained according to thepresent invention as a catalytic component.

1. Substituted cyclopentadiene represented by the following formula (2):

wherein A is a Group 16 element; B is a Group 14 element; R¹, R², R³ andR⁴ are the same or different and each independently denotes asubstituent selected from the group consisting of the following groups(I) and (II): group (I) consisting of hydrogen, substituted orunsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₆₋₂₀ aryl,substituted or unsubstituted C₇₋₂₀ aralkyl, and silyl substituted withsubstituted or unsubstituted C₁₋₂₀ hydrocarbon, and group (II)consisting of substituted or unsubstituted C₁₋₂₀ alkoxyl, substituted orunsubstituted C₆₋₂₀ aryloxy, substituted or unsubstituted C₇₋₂₀aralkyloxy, silyloxy substituted with substituted or unsubstituted C₁₋₂₀hydrocarbon, amino substituted with substituted or unsubstituted C₁₋₂₀hydrocarbon, phosphino substituted with substituted or unsubstitutedC₁₋₂₀ hydrocarbon, and thio substituted with substituted orunsubstituted C₁₋₂₀ hydrocarbon, provided that at least one of R¹, R²,R³ and R⁴ is a substituent group selected from the group (II); R⁵, R⁶,R⁷, R⁸, R⁹ and R¹⁰ are the same or different and each independentlydenotes hydrogen, halogen, substituted or unsubstituted C₁₋₂₀ alkyl,substituted or unsubstituted C₁₋₂₀ alkoxy, substituted or unsubstitutedC₆₋₂₀ aryl, substituted or unsubstituted C₆₋₂₀ aryloxy, substituted orunsubstituted C₇₋₂₀ aralkyl, substituted or unsubstituted C₇₋₂₀aralkyloxy, silyl substituted with substituted or unsubstituted C₁₋₂₀hydrocarbon, or amino substituted with substituted or unsubstitutedC₁₋₂₀ hydrocarbon; or two adjacent substituents of R¹, R², R³ and R⁴,and two adjacent substituents of R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰, may be eachoptionally bonded to form a ring; and R¹¹ is a substituted orunsubstituted hydrocarbon group or a tri-substituted silyl group.
 2. Aprocess of producing substituted cyclopentadiene represented by theformula (2) described in claim 1, which comprises reacting substitutedcyclopentadiene represented by the formula (5):

wherein R¹, R², R³ and R⁴ are the same or different and eachindependently denotes a substituent selected from the group consistingof the following groups (I) and (II): group (I) consisting of hydrogen,substituted or unsubstituted C₁₋₂₀ alkyl, substituted or unsubstitutedC₆₋₂₀ aryl, substituted or unsubstituted C₇₋₂₀ aralkyl, and silylsubstituted with substituted or unsubstituted C₁₋₂₀ hydrocarbon, andgroup (II) consisting of substituted or unsubstituted C₁₋₂₀ alkoxyl,substituted or unsubstituted C₆₋₂₀ aryloxy, substituted or unsubstitutedC₇₋₂₀ aralkyloxy, silyloxy substituted with substituted or unsubstitutedC₁₋₂₀ hydrocarbon, amino substituted with substituted or unsubstitutedC₁₋₂₀ hydrocarbon, phosphino group substituted with substituted orunsubstituted C₁₋₂₀ hydrocarbon, and thio substituted with substitutedor unsubstituted C₁₋₂₀ hydrocarbon, provided that at least one of R¹,R², R³ and R⁴ is a substituent group selected from the group (II); orthe two adjacent substituents of R¹, R², R³ and R⁴ may be optionallybonded to form a ring; with a base and then reacting with a compoundrepresented by the formula (6):

wherein A is a Group 16 element; B is a Group 14 element; X⁵ is ahalogen atom; R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are the same or different andeach independently denotes hydrogen, halogen, substituted orunsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₁₋₂₀ alkoxy,substituted or unsubstituted C₆₋₂₀ aryl, substituted or unsubstitutedC₆₋₂₀ aryloxy, substituted or unsubstituted C₇₋₂₀ aralkyl, substitutedor unsubstituted C₇₋₂₀ aralkyloxy, silyl substituted with substituted orunsubstituted C₁₋₂₀ hydrocarbon, or amino substituted with substitutedor unsubstituted C₁₋₂₀ hydrocarbon; or two adjacent substituents of R⁵,R⁶, R⁷, R⁸, R⁹ and R¹⁰ may be optionally bonded to form a ring; and R¹¹is a substituted or unsubstituted hydrocarbon group or a tri-substitutedsilyl group.